WO1999033771A1 - Procede de preparation de composes ayant des groupes -ch2-chf- - Google Patents

Procede de preparation de composes ayant des groupes -ch2-chf- Download PDF

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Publication number
WO1999033771A1
WO1999033771A1 PCT/JP1998/005958 JP9805958W WO9933771A1 WO 1999033771 A1 WO1999033771 A1 WO 1999033771A1 JP 9805958 W JP9805958 W JP 9805958W WO 9933771 A1 WO9933771 A1 WO 9933771A1
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group
compound
carbon atoms
reaction
production method
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PCT/JP1998/005958
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English (en)
Japanese (ja)
Inventor
Toshiro Yamada
Takashi Uruma
Tatsuya Sugimoto
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Nippon Zeon Co., Ltd.
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Priority to DE69830746T priority Critical patent/DE69830746T2/de
Priority to US09/582,325 priority patent/US6395700B1/en
Priority to EP98961602A priority patent/EP1043297B8/fr
Priority to JP2000526458A priority patent/JP4538953B2/ja
Publication of WO1999033771A1 publication Critical patent/WO1999033771A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C23/00—Compounds containing at least one halogen atom bound to a ring other than a six-membered aromatic ring
    • C07C23/02—Monocyclic halogenated hydrocarbons
    • C07C23/08—Monocyclic halogenated hydrocarbons with a five-membered ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
    • C07C17/20—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms
    • C07C17/202—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction
    • C07C17/208—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction the other compound being MX
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/23—Preparation of halogenated hydrocarbons by dehalogenation

Definitions

  • the present invention relates to a method for producing a compound having one CH 2 —CHF— group and having 4 or more carbon atoms, which is useful as a detergent or a solvent.
  • Hydrofluorocarbons that do not have chlorine atoms, which is a major cause of ozone depletion, are one type of CFC substitute. Hydrofluorocarbons are known to be chlorine-free, non-flammable and stable. In addition, it is known that when used as it is or in combination with an organic solvent, it provides excellent finishing cleaning performance.
  • Hydrofluorocarbons containing no chlorine atom include: — Hydrofluorocarbon compounds having one CH 2 —CHF group are expected as a new generation of fluorine-based materials. This fluor-carbon compound having a —CH 2 —CHF— group has no ozone depleting power because it does not contain chlorine atoms, and has the advantage of low global warming potential because of its short atmospheric life. It dissolves dirt components moderately, does not attack plastics, etc., has excellent stability to heat and chemicals, and is nonflammable.
  • a method for producing a chain hydrofluorocarbon compound having a CH 2 —CHF— group is conventionally known only for those having 3 carbon atoms.
  • Japanese Patent Application Laid-Open No. 8-33 7542 describes a method for producing CF 3 CH 2 CHF 2 by reacting CF 3 CC 1 CFCF 2 with hydrogen in the presence of a reduction catalyst.
  • these methods are inefficient in terms of introducing three hydrogens in two steps and preliminarily synthesizing a raw material in which chlorine atoms are selectively arranged at necessary sites, and there is a need for improvement. I got it.
  • 1,1,2,2,3,3,4-Heptanefluorocyclopentane which is an alicyclic hydrofluorocarbon compound having one or more CH 2 —CHF— groups and having 4 or more carbon atoms
  • a noble metal catalyst such as palladium
  • An object of the present invention is to provide a method for industrially and advantageously producing a compound having 4 or more carbon atoms having one CH 2 —CHF— group which is useful as a substitute for chlorofluorocarbons.
  • the present inventors have conducted intensive studies on this problem, and as a result, developed a method for obtaining the target product with high purity by utilizing the difference in the reactivity of hydrogen substitution between chlorine and fluorine atoms during the hydrogenation reaction. Was successful.
  • a method for producing a compound having 4 or more carbon atoms is provided.
  • the present invention further provides a method for producing a compound having 4 or more carbon atoms having one CH 2 and one CHF— group, wherein the compound is hydrogenated in the presence of a noble metal catalyst.
  • the compound to which the production method of the present invention can be applied is a compound containing a linear or alicyclic —CC 1 CFCF group, and is particularly suitably applicable to an alicyclic compound.
  • the carbon number of the basic skeleton of the compound containing one CC 1 -CF— group is usually 4 to 10, preferably 4 to 6, and most preferably 5.
  • Ri and R 2 each independently represent a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 8 carbon atoms. All or a part of the alkyl group having 1 to 8 carbon atoms may be fluorinated. However, at least one of Ri and R 2 is an optionally fluorinated alkyl group having 1 to 8 carbon atoms, and the sum of the carbon numbers of both Ri and R 2 is at least 2. In addition, Ri and R 2 combine to form a divalent hydrocarbon group having 2 to 8 carbon atoms — Ri — R 2 — and form an alicyclic compound together with Ci and C 2. Is also good. All or part of the hydrogen atoms of the divalent hydrocarbon group-Ri -R2-may be fluorinated.
  • perfluoroalkyl group having 1 to 8 carbon atoms include a perfluoromethyl group, a perfluoroethyl group, a perfluoro-n-propyl group, a perfluorosopropyl group, a perfluoro-n-butyl group, and a perfluoro-tert_ group.
  • Ri and R 2 in the formula (1) are bonded together to form a divalent hydrocarbon group having 2 to 8 carbon atoms — Ri _R2 —, and together with the carbon atoms Ci and C2, the following formula (2)
  • the indicated alicyclic compound may be formed.
  • the carbon number of the divalent hydrocarbon group —Ri—R2— is 2 to 8, preferably 2 to 4. Further, some or all of the hydrogen atoms in this group may be fluorinated, and preferably all are fluorinated.
  • perfluorofluoroalkylene groups having 2 to 8 carbon atoms and all of the hydrogen atoms of one hydrocarbon group Ri-R2 are fluorinated include, for example, perfluoroethylene group, perfluoro-n-propylene Group, perfluoroisopropylene group, perfluoro-n-butylene group, perfluoro-tert-butylene group, perfluoro-pentylene group, perfluoro-hexylene group, perfluoroheptylene group, perfluoro- And octylene groups.
  • the alicyclic compound of the formula (2) in which Ci, C 2 and the divalent hydrocarbon group —Ri—R 2 — of the formula (1) form a ring is, for example, a cyclobutene compound, a cyclopentene compound , Cyclohexene compounds, cycloheptene compounds, cyclooctene compounds, etc., preferably cyclobutene compounds, cyclopentene compounds, and cyclohexene compounds. It is a xen compound, more preferably a cyclopentene compound.
  • 1-chlorononafluoropentene 2-chlorononafluoropentene, 3-chlorononafluorene 1-pentene, 1-cyclopentene is preferred, and fluorocyclopentene is preferred. Fluorocyclopentene is most preferred.
  • the hydrogenation reaction will be described.
  • the noble metal catalyst used is a noble metal simple substance or a noble metal compound.
  • the noble metal catalyst is preferably used in a form supported on a carrier.
  • the noble metal examples include palladium, rhodium, ruthenium, rhenium, platinum, and the like. Among them, palladium, rhodium, and ruthenium are preferable, and palladium is most preferable.
  • the noble metal compound include salts such as palladium acetate, palladium sulfate, and palladium nitrate, and halides such as palladium chloride.
  • noble metal catalysts may be composed of a single metal, or two or more. It may be used as an alloy of the above metals, a so-called bimetallic catalyst. As the alloy, an alloy mainly containing palladium is preferable.
  • the type of carrier on which the noble metal catalyst is supported and the shape and size of the carrier are not particularly limited.
  • As the type of the carrier activated carbon, alumina, silica gel, titania, zirconia, and those obtained by treating these with hydrogen fluoride are preferable.
  • the shape of the carrier may be a powder or a granular material such as a sphere or a pellet.
  • the granular material may be a processed molded product or a crushed product.
  • the preferred form is powder for liquid phase reactions and granular for gas phase reactions.
  • the amount of precious metal supported on the carrier is usually
  • the preferred amount of the carrier is 0.1 to 20% by weight when the carrier is a powder, and 0.1 to 10% by weight when the carrier is a granular material. More preferably, in the case of a liquid phase reaction, it is a powder catalyst loaded with 1 to 10% by weight, and in the case of a gas phase reaction, it is a particulate catalyst loaded with 0.5 to 7% by weight.
  • a liquid phase reaction or a gas phase reaction is possible.
  • a solvent can be used in the liquid phase reaction.
  • a diluent can be used if necessary.
  • a fixed bed type gas phase reaction, a fluidized bed type gas phase reaction, and the like can be adopted in the gas phase reaction.
  • the solvent used in the liquid phase reaction is not particularly limited, and examples thereof include aliphatic hydrocarbons, aromatic hydrocarbons, fluorinated fluorocarbons, alcohols, ethers, ketones, esters, and water.
  • Aliphatic hydrocarbons usually have a carbon number of 4 to 15. Specific examples of the aliphatic hydrocarbons include n-butane, n-pentane, methylpentane, and n-hexane. , Cyclopentane, cyclohexane and the like.
  • aromatic hydrocarbons include trifluoromethylbenzene.
  • fluoridated hydrofluorocarbons include pentafluorene, pentafluoropropane, hexafluorobutane, and decafluoropentane.
  • Alcohols usually have 1 to 10 carbon atoms, preferably 1 to 10 carbon atoms. ⁇ 6. Specific examples of alcohols include methanol, ethanol, propanol, butanol, and cyclopentanol.
  • the ethers may have usually 4 to 10 carbon atoms, and preferably 4 to 6 carbon atoms. Specific examples of ethers include getyl ether, diisopropyl ether, and ethylene glycol dimethyl ether.
  • the ketones usually have 3 to 10 carbon atoms, preferably 3 to 8 carbon atoms. Specific examples of ketones include acetone, methyl ethyl ketone, methyl isopropyl ketone, methyl butyl ketone, and cyclopentanone.
  • the esters have usually 4 to 10 carbon atoms, preferably 4 to 8 carbon atoms. Specific examples of the esters include ethyl acetate, butyl acetate, propyl acetate, methyl propionate, methyl butyrate, and methyl valerate.
  • solvents may be used alone or in combination of two or more.
  • the diluent used in the gas phase reaction may be any gas that is inert to the present hydrogenation reaction, and specific examples include nitrogen gas, rare gas, hydrocarbon gas, and fluorinated carbon gas at the hydration port.
  • specific examples of the rare gas include argon gas and helium gas
  • specific examples of the hydrocarbon gas include methane gas, hydrogen gas, propane gas, and butane gas
  • specific examples of the fluorinated carbon gas at the hydrate port include: ⁇ ⁇ ⁇ ⁇ ⁇ , ⁇ ⁇ ⁇ ⁇ , ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ .
  • diluents may be used alone or in combination of two or more.
  • the pressure of the reaction system of the present hydrogenation reaction is usually from normal pressure to 50 kgf Z cm 2 , preferably from normal pressure to 20 kgf / cm 2 .
  • the reaction temperature is usually from room temperature to 350 And preferably about room temperature to about 200. In this reaction, if necessary, the inside of the reaction system is stirred or shaken.
  • the hydrogenation reaction of the present invention employs a batch reaction or a continuous reaction in which raw materials are continuously supplied to a reactor and a reaction product is continuously withdrawn from the reactor.
  • the reaction vessel used is a pressure vessel in the case of a batch reaction, and in a continuous reaction one or more reactors connected in series, for example a cascade reactor, can be used.
  • stainless steel is suitable.
  • acidic components such as hydrogen chloride gas are generated as by-products.
  • This acidic component is preferably absorbed or neutralized and removed during the reaction.
  • an additive may be added to the system.
  • the desired product can be isolated by a conventional purification method such as distillation after absorbing or neutralizing the acidic component with an additive, if necessary.
  • the compound obtained by the production method of the present invention is a compound having one CH 2 —CHF— group and having 4 or more carbon atoms.
  • the compound having 4 or more carbon atoms having a CH 2 —CHF — group obtained by hydrogenation is a linear or alicyclic compound, and the method of the present invention is particularly suitable for the synthesis of an alicyclic compound.
  • Applicable to The carbon number of the basic skeleton of the compound having one CH 2 —CHF— group is usually 4 to 10, preferably 4 to 6, and most preferably 5.
  • R3 and R4 are the same as R 1 and R 2 in the formula (1).
  • At least one of R3 and R4 is an optionally fluorinated alkyl group having 1 to 8 carbon atoms, and the sum of the carbon numbers of both R 3 and R 4 is at least 2; and R 3 and R 4 combine together to form a divalent hydrocarbon group having 2 to 8 carbon atoms, R 3 — R 4 —, which may form an alicyclic compound together with C 3 and C 4 This is the same as Ri and R2 in the above formula (1).
  • perfluoroalkyl groups having 1 to 8 carbon atoms for R 3 and R 4 are the same as those for R 1 and R 2 in the formula (1).
  • perfluoroalkylene group of 8 are the same as those of -Ri-R2- in the formula (1).
  • the compound having 4 or more carbon atoms having a —CH 2 —CHF— group is a linear or alicyclic compound.
  • chain compound having a —CH 2 —CHF— group examples include 1, 1,] 2,
  • 4,4,4_heptafluoro-n-butane 1 1 2 : 2 3 5 5,5-nonafluoro-n-pentane, 1,1,1 2 2 4 5 5 5 nonafluoro-n-pentane, 1,1, 1,2,2 3 3 4 6 6 6 1 Decafluoro n-hexane, 1,1,1,2 2 3 3 5 6 6 6 1 1 1 1 1 1 2 2 4 5 5 6, 6, 6-indene-fluorinated n-hexane and the like.
  • Specific examples of the alicyclic compound having a CH 2 —CHF _ group include 1,1,2,2,3-pentanofluorocyclobutane.
  • 1,1,2,2,3,3,4 hepnofluorocyclopentane, 1,1,2,2,3,3,4,4,5-nonafluorocyclohexane No.
  • Contains —CC 1 CF—group used as starting material in the above hydrogenation reaction
  • R5-C5 C 1 C 6 C 1 -Re formula (4)
  • R5 and R6 are the same as Ri and R2 in the formula (1). Further, an alkyl group of R5 and at least one of the number of carbon atoms, which may be fluorinated 1-8 of R 6, it is the sum of the carbon atoms of R5 and R 6 both are at least 2; and R5 And R 6 are bonded together to form a divalent hydrocarbon group having 2 to 8 carbon atoms —R 5 —R 6 — and may form a cyclic compound together with C 5 and C 6 according to the above formula ( 1) is the same as that of Ri you and R 2 of.
  • R5 and R 6 Specific examples of preferred paths one Furuoroarukiru group having 1 to 8 carbon atoms as R5 and R 6 are the same as Ri and R2 in the formula (1). Also, - R5 - R6 - Specific examples of the to preferred per full O b alkylene group having 2 to 8 carbon atoms, the formula (1) -Ri- R 2 - are the same as in the case of.
  • Examples include 1,2-dichlorotetrafluorocyclobutene-11,1,1,2-dichlorohexafluorocyclopentene-11,1,1,2-dichlorobutafluorocyclohexene-11, and the like.
  • the fluorinating agent is not particularly limited as long as it is a compound capable of releasing fluorine ions, but is usually a metal fluoride, anhydrous or aqueous hydrofluoric acid, or an association of hydrofluoric acid and an amine or a quaternary ammonium salt And an aggregate of hydrofluoric acid and a polar solvent.
  • metal fluorides are preferred.
  • metal fluoride examples include metal fluorides such as alkali metals, alkaline earth metals, and transition metals. Preferably, it is an alkali metal fluoride. Specific examples of the alkali metal fluoride include sodium fluoride, potassium fluoride, and lithium fluoride. Of these, potassium fluoride is preferred. These fluorinating agents may be used alone or in combination of two or more.
  • This reaction may be performed by a liquid phase reaction or a gas phase reaction.
  • a liquid phase reaction or a gas phase reaction.
  • the above-mentioned alkali metal fluoride is used, it is generally carried out in a liquid phase under normal pressure.
  • a solvent may be used.
  • an aprotic polar solvent is usually used.
  • Specific examples of such aprotic polar solvents include N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetoamide, N, N'-dimethylimidazolidinone and the like. Preferred are N-methylpyrrolidone and N, N-dimethylformamide. These solvents may be used alone or in combination of two or more. If necessary, aromatic hydrocarbons such as benzene, toluene, xylene, and mesitylene which are compatible with the above aprotic polar solvent can be used.
  • the reaction temperature in the liquid phase reaction can be appropriately selected in the range of 20 to 200.
  • a reaction vessel equipped with a rectification column it is preferable to use a reaction vessel equipped with a rectification column and perform the reaction in a solvent in which metal fluoride is dispersed.
  • a diluent may be used. Specific examples of the diluent used in the gas phase reaction include those similar to the above-mentioned solvents used in the liquid phase reaction.
  • the reaction temperature in the gas phase reaction can be appropriately selected from 100 T: to 500.
  • the fluorination reaction of the present invention employs a batch system or a continuous system in which raw materials are continuously supplied to a reactor and reaction products are continuously withdrawn from the reactor.
  • an alkali metal fluoride such as potassium fluoride
  • an alkali metal chloride such as a chloride chlorite is generated as a reaction by-product. After the completion of the reaction, this reaction by-product is removed by filtration or washing with water.
  • additives can be added to the system if necessary.
  • additives include hydroxides, oxides, weak acid salts, and organic acid salts of alkali metals or alkaline earth metals. Specific examples thereof include soda lime, quicklime, alkali carbonate, and alkali acetate. Is mentioned. These additives may be used alone or in combination of two or more.
  • the amount of the additive to be used is usually 1 equivalent or more based on the compound containing one C 1 -C 1 group.
  • 1,2-dichlorohexafluorocyclopentene 50.10 g, 0.205 mol
  • potassium fluoride 1.3.5 g, 0.225 mol
  • N, N-dimethyl Formamide 50 ml
  • Distillation of the product started 0.3 hours after the start of heating. After the distilling was completed, the internal pressure was reduced and the remaining product was collected in a cooling trap, and together with the distillate, washed with neutralized water with sodium bicarbonate water.
  • the obtained product was analyzed to find that the desired 1-fluorohexylcyclopentene was obtained in a yield of 79.1%.
  • the 1-chloro mouth heptafluorocyclopentene obtained above (15 g, 65.6 mmol), 5% palladium on carbon catalyst (5% by weight), sodium acetate (10.9 g) and water ( 25.0m 1) was charged into a pressure reactor and stirred under a hydrogen pressure of 10 kgf Zcm2. After 24 hours, the reaction solution was filtered to remove the catalyst, and then the organic phase was separated and washed with water. As a result of analyzing the product obtained after removing the remaining raw materials, 50% of the desired 1,1,2,2,3,3,4-fluorohexacyclopentane was obtained as a by-product. It was found that 1,1,2,2,3,3-hexafluorocyclopentane was formed at a rate of 40%.
  • 1,1,2,2,3,3,4-hepnofluorocyclopentane By rectifying this, the desired 1,1,2,2,3,3,4-hepnofluorocyclopentane could be isolated with a high purity of 98%.
  • the boiling point of 1,1,2,2,3,3,4-hepnofluorocyclopentane was 8076 OmmHg.
  • the boiling point of 1,1,2,2,3,3-hexafluorocyclopentane was 8 ⁇ / ⁇ 6 OmmHg.
  • Example 1 Liquid phase hydrogenation of fluorene alkenes.
  • Example 1 Example 1 was repeated except that sodium acetate and water were not used in the subsequent hydrogenation reaction, and that the reaction time was changed to 30 hours, as in Example 1. The reaction was carried out as in 1. Analysis of the reaction product from which residual raw materials had been removed revealed that the desired 1,1,2,2,3,3,4,1-fluorohexacyclopentane was 70%, and 1,1 as a by-product. It was found that 2,2,3,3-hexafluorocyclopentane was formed at a rate of 2%.
  • the mixture was placed in a 500 ml glass flask and heated to 110 ° C. at an internal temperature with stirring. Distillation of the product started 0.5 hours after the start of heating.
  • the product was extracted from the top of the distillation column at a reflux ratio of 10: 1, and collected in a receiver immersed in a bath of ice water and dry ice / acetone.
  • a 1/2 inch diameter, 15 cm long SUS 316 reaction tube equipped with an external electric furnace is filled with 5 ml of palladium catalyst (manufactured by Nikki Chemical) supported on alumina spheres at a concentration of 0.5%. And heated to 150. Pretreatment was performed by flowing hydrogen gas through this reaction tube in advance at 200 ml / min for 8 hours. After that, 1-chloro-2,3,3,4,4,5,5-hepnofluorocyclopentene was supplied at a rate of 0.1 ml / min to a vaporizer heated to 100 and then for 30 hours. The reaction was continued. The generated gas was washed with water, dried over calcium chloride, collected in a glass trap cooled to -78, and analyzed by gas chromatography.
  • palladium catalyst manufactured by Nikki Chemical
  • a reaction tube made of SUS316 with a diameter of 1Z2 inch and a length of 15cm equipped with an external electric furnace is filled with 5ml of palladium catalyst (manufactured by Nikki Chemical) supported on activated carbon at a concentration of 0.5%. And heated to 150. Pretreatment was performed by flowing hydrogen gas through this reaction tube at 200 m 1 / min in advance for 8 hours. After that, 1_black mouth—2,3,3,4,4,5,5-hepnofluorocyclopentene is supplied to the vaporizer heated to 10 O: at a rate of 0.1 lm for 1 minute, The reaction was continued for hours.
  • palladium catalyst manufactured by Nikki Chemical
  • the generated gas was washed with water, dried with chlorinated calcium chloride, collected in a glass trap cooled to ⁇ 78 ° C, and analyzed by gas chromatography.
  • the conversion of the raw material was 99%, 1,1,2,2,3,3,4,1-fluorofluorocyclopentane was 89%, 1,3,3,4,4,5, 4% of 5_hepnofluorocyclopentene and 6% of 1,1,2,2,3,3-hexafluorocyclopentane were formed.
  • Palladium catalyst supported on alumina spheres at a concentration of 0.5% (manufactured by JGC Chemicals, average particle size 3 mm) 50 ml was filled into a SUS316 reaction tube 2.54 cm in diameter and 40 cm in length, and 250 A nitrogen gas was flowed at a rate of 100 ml / min while heating to ° C. After drying for 2 hours, the temperature was further raised to 300, and gaseous hydrogen fluoride was supplied to the reaction tube at a rate of 400 m1Z. When generation of water was no longer observed, the supply of hydrogen fluoride was stopped, and nitrogen gas was flowed at a rate of 50 m1 / min to remove excess hydrogen fluoride.
  • the product a compound having one or more carbon atoms and having one CH 2 —CHF _ group, has no problem of depletion of the ozone layer, and therefore has a wide range of uses as a substitute for chlorofluorocarbons, as a cleaning agent or solvent.

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  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Composés ayant chacun un groupe -CH2-CHF- et au moins 4 atomes de carbone. On prépare lesdits composés en hydrogénant un composé ayant un groupe -CCl=CF- et au moins 4 atomes de carbone, en présence d'un catalyseur à base de métal noble, en phase liquide ou gazeuse. Le composé ayant le groupe -CCl=CF- et au moins 4 atomes de carbone est de préférence un composé alicyclique C4-C10 et peut être préparé par la mise en réaction d'un composé ayant un groupe -CCl=CCl- et au moins 4 atomes de carbone, avec un agent de fluoration.
PCT/JP1998/005958 1997-12-26 1998-12-25 Procede de preparation de composes ayant des groupes -ch2-chf- WO1999033771A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
DE69830746T DE69830746T2 (de) 1997-12-26 1998-12-25 Verfahren zur herstellung von verbindungen mit einem -ch2-chf- strukturelement
US09/582,325 US6395700B1 (en) 1997-12-26 1998-12-25 Process for the preparation of compounds having -CH2-CHF-groups
EP98961602A EP1043297B8 (fr) 1997-12-26 1998-12-25 Procede de preparation de composes ayant des groupes -ch2-chf-
JP2000526458A JP4538953B2 (ja) 1997-12-26 1998-12-25 −ｃｈ２−ｃｈｆ−基を有する化合物の製造方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP36754097 1997-12-26
JP9/367540 1997-12-26

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WO1999033771A1 true WO1999033771A1 (fr) 1999-07-08

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EP (1) EP1043297B8 (fr)
JP (1) JP4538953B2 (fr)
CN (1) CN1127462C (fr)
DE (1) DE69830746T2 (fr)
WO (1) WO1999033771A1 (fr)

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JP2000247912A (ja) * 1999-03-01 2000-09-12 Central Glass Co Ltd ヘプタフルオロシクロペンタンの製造方法
WO2010007968A1 (fr) * 2008-07-18 2010-01-21 日本ゼオン株式会社 Procédé de fabrication d'un composé d'oléfine fluorée contenant de l'hydrogène
WO2014129488A1 (fr) * 2013-02-21 2014-08-28 日本ゼオン株式会社 1h-heptafluorocyclopentène à pureté élevée
CN114605224A (zh) * 2022-01-29 2022-06-10 国网湖南省电力有限公司 一种1,1,2,2,3,3,4-七氟环戊烷及其制备方法和应用
EP4032533A1 (fr) 2012-07-10 2022-07-27 The Regents of The University of California Méthodes pour induire une anesthésie

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US7902410B2 (en) * 2005-11-03 2011-03-08 Honeywell International Inc. Process for the manufacture of fluorinated alkanes
US8618339B2 (en) * 2007-04-26 2013-12-31 E I Du Pont De Nemours And Company High selectivity process to make dihydrofluoroalkenes
US8158549B2 (en) * 2009-09-04 2012-04-17 Honeywell International Inc. Catalysts for fluoroolefins hydrogenation
CN105601468B (zh) * 2015-10-22 2017-07-25 北京宇极科技发展有限公司 同时制备二氯六氟环戊烯同分异构体的方法
CN106995362B (zh) * 2017-05-16 2020-02-18 北京宇极科技发展有限公司 七氟环戊烯的制备方法

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US8318991B2 (en) 2008-07-18 2012-11-27 Zeon Corporation Method for producing hydrogen-containing fluoroolefin compound
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KR101592056B1 (ko) * 2008-07-18 2016-02-05 제온 코포레이션 함수소 플루오로올레핀 화합물의 제조 방법
EP4032533A1 (fr) 2012-07-10 2022-07-27 The Regents of The University of California Méthodes pour induire une anesthésie
WO2014129488A1 (fr) * 2013-02-21 2014-08-28 日本ゼオン株式会社 1h-heptafluorocyclopentène à pureté élevée
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JP4538953B2 (ja) 2010-09-08
CN1127462C (zh) 2003-11-12
EP1043297B1 (fr) 2005-06-29
DE69830746D1 (de) 2005-08-04
EP1043297B8 (fr) 2005-09-07
EP1043297A4 (fr) 2003-07-09
EP1043297A1 (fr) 2000-10-11
CN1286672A (zh) 2001-03-07
US6395700B1 (en) 2002-05-28

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